气候变化领域集成服务门户(CCPortal): Role of intramolecular hydrogen bonds in promoting electron flow through amino acid and oligopeptide conjugates

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DOI	10.1073/PNAS.2026462118
	Role of intramolecular hydrogen bonds in promoting electron flow through amino acid and oligopeptide conjugates
	Orlowski R.; Clark J.A.; Derr J.B.; Espinoza E.M.; Mayther M.F.; Staszewska-Krajewska O.; Winkler J.R.; Jedrzejewska H.; Szumna A.; Gray H.B.; Vullev V.I.; Gryko D.T.
发表日期	2021
ISSN	00278424
卷号	118 期号:11
英文摘要	Elucidating the factors that control charge transfer rates in relatively flexible conjugates is of importance for understanding energy flows in biology as well as assisting the design and construction of electronic devices. Here, we report ultrafast electron transfer (ET) and hole transfer (HT) between a corrole (Cor) donor linked to a perylene-diimide (PDI) acceptor by a tetrameric alanine (Ala)4. Selective photoexcitation of the donor and acceptor triggers subpicosecond and picosecond ET and HT. Replacement of the (Ala)4 linker with either a single alanine or phenylalanine does not substantially affect the ET and HT kinetics. We infer that electronic coupling in these reactions is not mediated by tetrapeptide backbone nor by direct donor-acceptor interactions. Employing a combination of NMR, circular dichroism, and computational studies, we show that intramolecular hydrogen bonding brings the donor and the acceptor into proximity in a "scorpion-shaped" molecular architecture, thereby accounting for the unusually high ET and HT rates. Photoinduced charge transfer relies on a (Cor)NH...O=C-NH...O=C(PDI) electronic-coupling pathway involving two pivotal hydrogen bonds and a central amide group as a mediator. Our work provides guidelines for construction of effective donor-acceptor assemblies linked by long flexible bridges as well as insights into structural otifs for mediating ET and HT in proteins. © 2021 National Academy of Sciences. All rights reserved.
英文关键词	Charge transfer; Corrole; Folding; Hydrogen bonding; Perylene diimide
语种	英语
来源期刊	Proceedings of the National Academy of Sciences of the United States of America
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/180312
作者单位	Institute of Organic Chemistry, Polish Academy of Sciences, Warsaw, 01-224, Poland; Department of Bioengineering, University of California, Riverside, CA 92521, United States; Department of Biochemistry, University of California, Riverside, CA 92521, United States; Department of Chemistry, University of California, Riverside, CA 92521, United States; Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, United States; College of Bioengineering, University of California, Berkeley, CA 94720, United States
推荐引用方式 GB/T 7714	Orlowski R.,Clark J.A.,Derr J.B.,et al. Role of intramolecular hydrogen bonds in promoting electron flow through amino acid and oligopeptide conjugates[J],2021,118(11).
APA	Orlowski R..,Clark J.A..,Derr J.B..,Espinoza E.M..,Mayther M.F..,...&Gryko D.T..(2021).Role of intramolecular hydrogen bonds in promoting electron flow through amino acid and oligopeptide conjugates.Proceedings of the National Academy of Sciences of the United States of America,118(11).
MLA	Orlowski R.,et al."Role of intramolecular hydrogen bonds in promoting electron flow through amino acid and oligopeptide conjugates".Proceedings of the National Academy of Sciences of the United States of America 118.11(2021).